The present invention relates to propylene polymers incorporating macromers and a method for the preparation of branched polypropylene utilizing chiral, stereorigid transition metal catalyst compounds.
Polypropylene and related polymers are known to have low melt strength. This is a significant deficiency in key application areas such as thermoforming, blow molding, and fiber spinning. Polyethylene on the other hand is used extensively in blown film applications requiring good melt strength. The limitations in the melt strength of polypropylenes show up as excess sag in sheet extrusion, rapid thinning of walls in parts thermoformed in the melt phase, low draw-down ratios in extrusion coating, poor bubble formation in extrusion foam materials, and relative weakness in large-part blow molding. Thus, it would be highly desirable to produce polypropylene and related polymers having enhanced melt strength as well as commercially valuable processability.
Increasing the melt strength of polymers such as polypropylene has been an industrial goal for well over ten years, however, success has been limited. The desirable properties that have made low density polyethylene commercially successful are attributed in large part to high melt strength and excellent processability. Both of these properties are attributed to the presence of long chain branching which is thought to occur under high pressure polymerization conditions.
There has been some success in increasing the melt strength of polypropylene. For example, EP 190 889 A2 discloses high energy irradiation of polypropylene to create what is believed to be polypropylene having substantial free-end long branches of propylene units. EP 384 431 discloses the use of peroxide decomposition of polypropylene in the substantial absence of oxygen to obtain a similar product.
Other attempts to improve the melt properties of polypropylene include U.S. Pat. No. 5,541,236, which introduces long chain branching by bridging two PP backbones to form H-type polymers, and U.S. Pat. No. 5,514,761, which uses dienes incorporated in the backbones to achieve a similar effect. However, it is difficult to avoid cross-linking and gel formation in such processes.
Thus, there is still a need for propylene polymers having improved melt strength and good processability.
The present invention meets that need by providing a polyolefin product which comprises a branched olefin copolymer having an isotactic polypropylene backbone, polyethylene branches and, optionally, one or more comonomers. The total comonomer content of the branched olefin copolymer is from 0 to 20 mole percent. Also, the mass ratio of the isotactic polypropylene to the polyethylene ranges from 99.9:0.1 to 50:50. Additionally, a process is provided for preparing a branched olefin copolymer which comprises:
a) copolymerizing ethylene, optionally with one or more copolymerizable monomers, in a polymerization reaction under conditions sufficient to form copolymer having greater than 40% chain end-group unsaturation;
b) copolymerizing the product of a) with propylene and, optionally, one or more copolymerizable monomers, in a polymerization reactor under suitable polypropylene polymerization conditions using a chiral, stereorigid transition metal catalyst capable of producing isotactic polypropylene; and
c) recovering a branched olefin copolymer.
One invention embodiment relates to a polyolefin product comprising a branched olefin copolymer having an isotactic polypropylene backbone, optionally comprising mer units from one or more comonomers, and sidechains. These side chains are derived from macromers which have vinyl ends and are olefin copolymer chains having a number average molecular weight (Mn) of about 1500 to 25,154, the number average molecular weight being determined by gel permeation chromatography (GPC) at 145xc2x0 C. Additionally, the ratio of vinyl groups to total olefin groups in these side chains follows the formula: (vinyl groups/olefin groups)xe2x89xa7(comonomer mole percentage+0.1)axc3x9710axc3x97b. a and b take the following sets of values: a =xe2x88x920.24, b=0.8; a=xe2x88x920.20, b=0.8; a=xe2x88x920.18, b=0.83; a=xe2x88x920.15, b=0.83; or a=xe2x88x920.10, b=0.85. The total number of vinyl groups per 1000 carbon atoms is greater than or equal to 8000÷Mn in these macromers. The number of vinyl groups is determined by 1H-NMR at 125xc2x0 C. Mw/Mn ranges from 2.083 to 5.666.
Another invention embodiment relates to a polyolefin product comprising a branched olefin copolymer having an isotactic polypropylene backbone, optionally comprising mer units from one or more comonomers, and sidechains. These side chains are derived from macromers which have vinyl ends and are olefin copolymer chains having a number average molecular weight (Mn) of about 1500 to 75,000, the number average molecular weight being determined by gel permeation chromatography (GPC) at 145xc2x0 C. Additionally, the ratio of vinyl groups to total olefin groups in these side chains follows the formula: (vinyl groups/olefin groups)xe2x89xa7(comonomer mole percentage +0.1)axc3x9710axc3x97b. a and b take the following sets of values: a=xe2x88x920.24, b=0.8; a=xe2x88x920.20, b=0.8; a=xe2x88x920.18, b=0.83; a=xe2x88x920.15, b=0.83; or a=xe2x88x920.10, b=0.85. The total number of vinyl groups per 1000 carbon atoms is greater than or equal to 8000÷Mn in these macromers. The number of vinyl groups is determined by 1H-NMR at 125xc2x0 C. Mw/Mn ranges from 2.083 to 5.666. Finally, the vinyl ended olefin copolymer chains are prepared from ethylene and at least one monomer selected from C3 to C12 xcex1-olefins.